synthetic methods of organometallic and inorganic
TRANSCRIPT
Synthetic Methods of Organometallic and Inorganic Chemistry (Herrmann/Brauer)
Volume 10 Catalysis
Volume Editor: Wolfgang A. Herrmann
24 Figures, 31 Tables
Georg Thieme Verlag Stuttgart • New York 2002
Contents
Chapter 1 A m i d o L igands in Coordinat ion Chemistry Thomas Schareina, Rhett Kempe 1
1.1 Introduction 2
1.2 Amidinates 3 1.2.1 Ligands 3 1.2.2 Group 3 Metal and Lanthanide Complexes 4 1.2.3 Titanium and Zirconium Complexes 8 1.2.4 Complexes of the Vanadium Triad 12 1.2.5 Group 6 Metal and Later Transition Metal Complexes 14
1.3 Aminopyridinates 23 1.3.1 Ligands 23 1.3.2 Group 3 Metal and Lanthanide Complexes 25 1.3.3 Titanium and Zirconium Complexes 28 1.3.4 Complexes of the Vanadium Triad 34 1.3.5 Late Transition Metal Complexes 38 1.3.6 Heterobimetallics 40
Chapter 2 Hydroformylat ion and Hydroxycarbonyla t ion of Alkenes; Format ion of C-N and C-C B o n d s Paul C. J. Kamer, Gino P. F. van Strijdonck, Joost N. H. Reek, Piet W. N. M. van Leeuwen 42
2.1 Introduction 43 2.1.1 Synthesis of Tris(2-ferf.-butyl-4-methylphenyl) Phosphite 43 2.1.2 The Hydroformylation Process 43
2.2 Asymmetrie Hydroformylation of Styrene 45 2.2.1 Synthesis of Chiral Diphosphite 4 and its Complex HRh(4)(CO)2 45 2.2.2 Asymmetrie Hydroformylation 48
2.3 Palladium-Catalyzed Biphasic Hydroxycarbonylation of Alkenes 50 2.3.1 Preparation of Catalysts 50 2.3.2 Hydroxycarbonylation of Alkenes 51
2.4 Rhodium-Catalyzed Hydroformylation of Internal Olefins to Linear Aldehydes 53 2.4.1 Synthesis of Phosphine Ligands 54 2.4.2 Hydroformylation of Internal Alkenes 57
2.5 Application of (PP)Pd(Ar)(X) Catalysts in the Amination of Aryl Bromides 58 2.5.1 Preparation of Catalysts 59 2.5.2 Palladium-Catalyzed Coupling of 2-Methoxyaniline (o-Anisidine) with Bromo-
benzene 60
2.6 Fast Heck Reaction using Bulky Monodentate Phosphorus Ligands 61 2.6.1 Synthesis of [(Phosphorus Amidite)Pd(|a-Br)(p-C6H4CN)}2 61 2.6.2 Palladium-Catalyzed Coupling of Styrene with Iodobenzene 62
x Contents
Chapter 3 R h o d i u m Atom-Der ived Catalysts in the Hydroformylat ion of 1,3-Dienes and Hydros i ly lat ion of A r o m a t i c Nitri les Giovanni Vitulli, Paolo Pertici, Sergio Bertozzi, Anna Maria Caporusso, Raffaelli Lazzaroni, Piero Salvadori 64
3.1 Introduction 65
3.2 Preparation of the Catalysts 65 3.2.1 Rhodium Solvated Metal Atoms: Catalyst A 65 3.2.2 Rhodium Dust: Catalyst B 66 3.2.3 Rhodium ony-Al203 : Catalyst C 66
3.3 Hydroformylation of 1,3-Dienes with Rhodium Solvated Metal Atoms - Catalyst A 66
3.4 Hydrosilylation of Aromatic Nitriles with Rhodium Dust and Rhodium on y-A^C^ 68
Chapter 4 In Situ Catalysts in Enantiose lect ive Organic Transformat ions Henri Brunner 72 4.1 Introduction 73
4.2 Enantioselective Hydrogenation ofZ-(a)-./V-Acetamidocinnamic Acid 73
4.3 Enantioselective Hydrosilylation of Acetophenone with Diphenylsilane 74
4.4 Enantioselective Synthesis of 4-Phenyldeltacyclene 76
Chapter 5 Enantioselective Hydrogenations Hans-Ulrich Blaser, Benoit Pugin, Felix Spindler, Martin Struder 78
5.1 Application of Solvias Josiphos Complexes for the Enantioselective Hydrogenation ofSelectedC=N,C=CandC=Ofunctions 79
5.1.1 Introduction 79 5.1.2 Catalysts 79 5.1.3 Hydrogenation Procedure 80 5.1.4 Discussion 81 5.1.5 Conclusions 83
5.2 Immobilized Rh- and Ir-Diphosphine Complexes for Enantioselective Hydrogenation 83 5.2.1 Introduction 83 5.2.2 Immobilization of Functionalized Diphosphine Ligands 83 5.2.3 Discussion of Immobilized Catalysts 86 5.2.4 Catalyst Precursors 87 5.2.5 Hydrogenation Procedures 87 5.2.6 Discussion of Hydrogenation Reactions 89
5.3 Application of Cinchona-Modified Pt/Al203 Catalysts for the Enantioselective Hydrogenation of a-Functionalized Ketones 90
5.3.1 Introduction 90 5.3.2 Catalyst Types and Pretreatment 90 5.3.3 Modifiers 91
Contents xi
5.3.4 Hydrogenation Procedure 92 5.3.5 Scope of the Method 92
Chapter 6 Application of Cp*-Ruthenium(II) Catalysts in Stereoselective Hydrogenation of Sorbic Acid Birgit Drießen-Hölscher 94
6.1 Introduction 95
6.2 (Pentamethylcyclopentadienyl)ruthenium(r|4-Sorbic Acid) Triflate and (Pentamethyl-cyclopentadienyl)ruthenium(r|4-Sorbic Acid) Tetrakis[3,5-bis(trifluoromethyl)-phenyl]borate 95
6.3 Stereoselective Hydrogenation of Sorbic Acid (2) and Sorbic Alcohol 96
Chapter 7 Syn thes i s and Catalyt ic Appl icat ion of 1 ,6-Diene-Pal ladium(0) M o n o p h o s p h i n e Complexes Mario Gömez Andren, Alexander Zapf, Matthias Beller 99
7.1 Introduction 100
7.2 Synthesis of 1,6-Diene-Palladium(0) Monophosphine Complexes 100
7.3 Suzuki Coupling of Aryl Chlorides and Phenylboronic Acid 101
Chapter 8 C a t a l y z e d R e a c t i o n s of A r y l Hai ides Adrino F. Indolese, Anita Schynder 105
8.1 Pd-Catalyzed Synthesis of Primary Aromatic Amides from Aryl Halides 106 8.1.1 Introduction 106 8.1.2 Catalysts 106 8.1.3 TheReaction 107 8.1.4 Scope of the Method 107 8.1.5 Variations in the Procedure 107
8.2 Suzuki Reaction of Aryl Chlorides Catalyzed by Ni-Phosphine Complexes 109 8.2.1 Introduction 109 8.2.2 Catalyst Precursors 109 8.2.3 TheReaction 109 8.2.4 Scope of the Method 110 8.2.5 Variations in the Procedure 110
8.3 Pd-Catalyzed Coupling of oMalononitrile with Aryl Bromides 111 8.3.1 Introduction 111 8.3.2 Catalyst Precursors 111 8.3.3 TheReaction 111 8.3.4 Scope of the Method 112 8.3.5 Variations in the Procedure 112
xii Contents
Chapter 9 An Easy-To-Use Heterogeneous Catalyst for the Knoevenagel Condensation Bernd Siebenhaar, Bruno Casagrande 114
9.1 Introduction 115
9.2 Catalysts 115
9.3 TheReaction 115
9.4 ScopeoftheMethod 115
Chapter 10 Oxidative Functionalization of Methane and Other Alkanes Catalyzed by Vanadium Complexes Containing Pyrazole-2-carboxylato Ligands Georg Süss-Fink 117
10.1 Introduction 118
10.2 Catalysts 118
10.3 Oxidative Functionalization of Methane 119
10.4 Oxidative Functionalization of Cyclohexane 120
Chapter 11 Hydrogenation of Benzene and Benzene Derivatives Catalyzed by Cationic Arene Ruthenium Clusters under Biphasic Conditions Georg Süss-Fink 122
11.1 Introduction 123
11.2 Catalysts 123
11.3 Hydrogenation of Benzene and Benzene Derivatives 124
Chapter 12 Synthesis and Catalytic Applications of Re(VII) and Mo(VI) Oxo Complexes Wolfgang A. Herrmann, Richard W. Fischer, Michelle Groarke, Fritz E. Kühn 127
12.1 Synthesis of Organotrioxorhenium(VH) Complexes 128 12.1.1 Syntheses of Methyltrioxorhenium(VII) (MTO; CH3Re03) 128 12.1.2 Syntheses of Alkylrhenium (VII) Trioxides, RRe03 132 12.1.3 Syntheses of Cyclopentadienyltrioxorhenium(VII), (C5H5)Re03, and Derivatives 134
12.2 Alkyltrioxorhenium Lewis-Base Adducts 134 12.2.1. The Quinuclidine Adducts as Examples for Aliphatic Lewis Base Adducts 135 12.2.2 The Pyrazole Adducts as Examples for Aromatic Lewis Base Adducts 135
12.3 Organorhenium(VII)peroxo Complexes 136 12.3.1 Methyl(oxo)di(n2-peroxo)rhenium(VII) Hydrate 136 12.3.2 Synthesis of Diglyme Adducts of Methyl(oxo)di(-n2-peroxo)rhenium(VII) Hydrate
and u-Oxobis[aquo(oxo)diperoxorhenium(VII)] 137
Contents xiii
12. 4 Catalysis Mediated by Alkylrhenium Trioxides 138 12.4.1 Oxidation of Olefins using MTO as Catalyst 139 12.4.2 Oxidation of Aromatic Compounds 142 12.4.3 Oxidation of Native Starch [Oxidation of-C(6)H2OH to a Carboxyl Group] 143
12. 5 Synthesis and Applications of Octahedral DioxomoIybdenum(VI) Complexes 143 12.5.1 Synthesis of Lewis-Base Adducts of Dihalodioxomolybdenum(VI) and Application
in Olefin-Epoxidation 144 12.5.2. Synthesis of Lewis-Base Adducts of Dimethyldioxomolybdenum(VI) and Application
in Olefin-Epoxidation 146
Chapter 13 Synthesis and Application of Organyl-Cobalt Cocyclization Catalysts H. Bönnemann, W. Brijoux 149
13.1. Introduction 150
13.2. Pyridines 150 13.2.1. Alkyl- and Alkenylpyridines 150 13.2.2 a-Amino- and a-Alkylthiopyridines 153 13.2.3 Bipyridyls 154
13.3 Preparation of the Catalysts 155 13.3.1 r|5-Cyclopentadienyl-Co(cod) 155 13.3.2 r)5-Trimethylsilylcyclopentadienyl-Co(cod) 156 13.3.3 r|5-Indenyl-Co(cod) 156 13.3.4 ri6-l-Phenylborininato-Co(cod) 157
Chapter 14 Polymerization Reactions Fritz E. Kühn, Wen-MeiXue 158
14.1 Solvent-Stabilized Transition Metal Cations as Initiators for Cyclopentadiene Polymerization 159
14.2 Polymerization Experiments 161
14.3 Synthesis of the Initiators 161
Chapter 15 Catalysts for Alkene Polymerization HelmutG. Alt 167
15.1 Metallacyclic Metallocene Complexes as Catalysts for Ethylene Polymerization 168 15.1.1 Introduction 168 15.1.2 Synthesis of the Catalysts 168 15.1.3 Polymerization of Ethylene 169
XIV Contents
15.2 Synthesis of Bridged Bis(fluorenyl) Complexes of Zirconium and Their Application for Homogeneous Ethylene Polymerization 170
15.2.1 Introduction 170 15.2.2 Synthesis of the Catalysts 171 15.2.3 Homogeneous Polymerization of Ethylene 172
15.3 Application of Self-Immobilizing Metallocene Catalysts For Ethylene Polymerization 174
15.3.1 Introduction 174 15.3.2 Synthesis of the Catalysts 174 15.3.3 Ethylene Polymerization with Self-Immobilizing Catalysts 176
15.4 Synthesis of Various Substituted aMsa-Cyclopentadienyl-Fluorenyl Complexes of Zirconium and Their Application for Homogeneous Propene Polymerization 177
15.4.1 Introduction 177 15.4.2 Synthesis of the Catalysts 177 15.4.3 Syndiospecific Polymerization of Propene 178
Chapter 16 Application of Cationic Nickel(II) Complexes with Biphosphine Monoxide Ligands Ph2P(CH2)nP(0)Ph2 (n = 1 - 3) in Ethylene Oligomerization Peter Wasserscheid 180
16.1 Introduction 181
16.2 Synthesis of the Catalysts 181
16.3 Ethylene Oligomerization 183
Chapter 17 Bridged Cyclopentadienyl-Fluorenyl Zirconocenes and Their Use in the Polymerization of Propylene Abbas Razavi, Kai Hortmann, Vincenzo Bellia 185
17.1 Synthesis of Bridged, Unsubstituted Cyclopentadienyl-Fluorenyl Zirconocenes 186
17.2 Synthesis of Cationic Cyclopentadienyl-Fluorenyl Zirconocenes 187
17.3. Synthesis of Bridged, Substituted Cyclopentadienyl-Fluorenyl Zirconocenes 188
17.4 Polymerization with Bridged Cyclopentadienyl-Fluorenyl Zirconocenes 190 17.4.1 Polymerization Mechanisms 191 17.4.2 Polymerization Procedure 193
Chapter 18 Application of Palladium(II) Diphosphine Catalysts in the Alternating Copolymerization of Ethene with Carbon Monoxide Claudio Bianchini, Andrea Meli 194
18.1 Introduction 195
18.2 Copolymerization of Ethene with CO in Methanol 196
Contents xv
18.3 Copolymerization of Ethene with CO in Water 197
18.4 Terpolymerization of Ethene and Propene with CO in Water 199
18.5 Copolymerization of Ethene with CO in Dichloromethane 202
Chapter 19 Applications of Palladium Catalysts in the Polymerization of Ethene/Carbon Monoxide and Telomerization of Butadiene/Ammonia Birgit Drießen-Hölscher 202
19.1 Application of Cationic [(Allyl)palladium(PAS)] Catalysts in the Polymerization of Ethene and Carbon Monoxide 203
19.1.1 Synthesis of {(r|3-Allyl)[bis(diphenylphosphino)methane monosulfide-K2"P,5]-palladium(II)} Tetrafluoroborate 203
19.1.2 Polymerization of Ethene and Carbon Monoxide 204
19.2 Application of Water-Soluble Palladium Catalysts in the Telomerization of Butadiene and Ammonia 205
19.2.1 Synthesis of ri3-Allyl(diammo)palladium(II) Tetrafluoroborate 205 19.2.2 Telomerization of Butadiene and Ammonia 206
Chapter 20 Manufacture of Heterogeneous Mono- and Bimetallic Colloid Catalysts and Their Applications in Fine Chemical Synthesis and Fuel Cells Helmut Bönnemann, Ryan Richards 209
20.1 Introduction 210
20.2 Synthesis of Pt Precursors 211
20.3 Application of Colloidal Pt/C for the Selective Hydrogenation of 3,4-Dichloronitrobenzene 213
20.3.1 PreparationofthePtHydrosols 214 20.3.2 Preparation of Colloidal Pt/Activated Carbon Catalysts 216 20.3.3 Hydrogenation of 3,4-Dichloronitrobenzene 216
20.4 Applications in Catalysis 217 20.4.1 Preparation of the Colloids and Catalysts 218 20.4.2 Adsorption ofthe Colloids on the Support 219 20.4.3 CatalyticOxidationofGlucose 220 20.4.4 Hydrogenation of 3-Hexyn-l-ol 220
20.5 Application of Colloidal Pt/Ru/Vulcan as Fuel Cell Catalysts 221 20.5.1 Preparation ofthe Catalyst Precursors 222 20.5.2 Preparation of Fuel Cell Catalysts 223
Index 225